Density Functional Studies of the Reaction of Ytterbium Monocation with Fluoromethane:C-F Bond Activation and Electron-Transfer Reactivity  

作　　者：Dong Ju ZHANG Cheng Bu LIU 

机构地区：[1]Institution of Theoretical Chemistry,Shandong University,Ji nan 250100

出　　处：《Chinese Chemical Letters》2002年第4期359-362,共4页中国化学快报(英文版)

基　　金：supported by the National Science Foundation of Shandong Province(No.Z2000B02).

摘　　要：The potential energy surface and reaction mechanism corresponding to the reaction of ytterbium monocation with fluoromethane, which represents a prototype of the activation of C-F bond in fluorohydrocarbons by bare lanthanide cations, have been investigated for the first time by using density functional theory. A direct fluorine abstraction mechanism was revealed, and the related thermochemistry data were determined. The electron-transfer reactivity of the reaction was analyzed using the two-state model, and a strongly avoided crossing behavior on the transition state region was shown. The present results support the reaction mechanism inferred from early experimental data and the related thermochemistry data can provide a guide for further experimental researches.The potential energy surface and reaction mechanism corresponding to the reaction of ytterbium monocation with fluoromethane, which represents a prototype of the activation of C-F bond in fluorohydrocarbons by bare lanthanide cations, have been investigated for the first time by using density functional theory. A direct fluorine abstraction mechanism was revealed, and the related thermochemistry data were determined. The electron-transfer reactivity of the reaction was analyzed using the two-state model, and a strongly avoided crossing behavior on the transition state region was shown. The present results support the reaction mechanism inferred from early experimental data and the related thermochemistry data can provide a guide for further experimental researches.

关 键 词：C-F bond activation electron transfer ytterbium monocation fluoromethane DFT 

分 类 号：O643.1[理学—物理化学]